201202393 六、發明說明： 【發明所屬之技術領域】 本發明有關於特別是可使用作爲螢光燈之藍色發光源 之矽酸鹽系藍色發光螢光體以及製造該矽酸鹽系藍色發光 螢光體之有利方法。 【先前技術】 螢光燈等之藉由利用水銀蒸氣之放電而生成之紫外線 (波長：254nm)而激發螢光體並發出可見光之發光裝置中 ，藍色光之發光源已廣泛利用以（Ba，Eu)0 · MgO · 5Al2〇3 之通式表示之鋁酸鹽系之BAM藍色發光螢光體。然而， B AM藍色發光螢光體有經時發光強度降低較大的問題。 另一方面，作爲經時發光強度降低較小的藍色發光螢 光體，已知有以3(Me，Eu)0. aMgO· bSi02(但Me爲自 Ca、Sr及Ba所成組群選出之一種以上之鹼土類金屬，a 爲0.9~1.1範圍之數，b爲1.8~2.2範圍之數）之通式表示 之矽酸鹽系之藍色發光螢光體。然而，矽酸鹽系藍色發光 螢光體一般之發光強度低於鋁酸鹽系之BAM藍色發光螢 光體。 專利文獻1中，記載有於母體中含有Cu、Ga、Ge、 As、Ag、Cd、In、Sn、Sb、Au、Hg、T1、Pb、Bi 等元素 作爲添加元素之矽酸鹽系藍色發光螢光體，其以波長 1 4 7nm之真空紫外線激發時之發光強度較高。又，於該專 利文獻1之實施例，係藉由令使用SrC03作爲MeO源， 201202393 使用MgC03作爲MgO源，使用Si02作爲Si02源，使用 Eu203作爲EuO源，使用NH4Br作爲熔融助劑（助熔劑）之 粉末混合物予以燒成而製造矽酸鹽系藍色發光螢光體。 於專利文獻2中，主要記載有將Mg之一部分取代爲 自5族及6族之元素所成組群選出之金屬的矽酸鹽系藍色 發光螢光體，以波長14 6nm之真空紫外線照射1小時及 24小時時之發光強度獲得提高。又該專利文獻2之實施 例中，係將使用碳酸鋇及碳酸緦作爲MeO源，使用鹼性 碳酸鎂作爲MgO源，使用二氧化矽作爲Si02源，使用氧 化銪作爲EuO源之粉末混合物予以燒成，藉此製造矽酸 鹽系藍色發光螢光體。 [先前技術文獻] [專利文獻] 專利文獻1 :特開2006-70 1 87號公報 專利文獻2 :特開2007-3 1 4644號公報 【發明內容】 [發明欲解決之課題] 如上述，以提高矽酸鹽系藍色發光螢光體之發光元件 的發光強度爲目的雖已進行各種探討，但若依據本發明人 之探討，則迄今已知之矽酸鹽系藍色發光螢光體以尤其是 波長25 4nm之紫外線激發時之發光強度，與BAM藍色螢 光體相較，尙無法稱爲已充分提高之程度。 .201202393 因此’本發明之目的系提供以波長2 5 4nm之紫外線 激發時之藍色光發光強度獲得提高之矽酸鹽系藍色發光螢 光體以及其製造方法。 [用以解決課題之手段] 本發明人發現於將含有MeO源粉末、EuO源粉末、 MeO源粉末及Si02源粉末之粉末混合物予以燒成而製造 矽酸鹽系藍色發光螢光體時，於MgO源係使用使金屬鎂 蒸氣與氧接觸而使金屬鎂蒸氣氧化之方法所得之高純度之 微細氧化鎂粉末，或者於MgO源使用高純度之微細鹼性 碳酸鎂粉末，進而於粉末混合物中添加特定量之氯化合物 作爲助熔劑，藉此所得之矽酸鹽系藍色發光螢光體以波長 2 54nm之紫外線激發時之發光強度獲得提高，尤其可獲得 發光強度爲鋁酸鹽系之 BAM藍色發光螢光體以波長 254nm之紫外線激發時之發光強度的1.1倍以上之新穎矽 酸鹽系藍色發光螢光體，因而完成本發明。 因此，本發明之以下述式（I)之組成式表示之矽酸鹽 系藍色發光螢光體之製造方法，其特徵爲使含有純度爲 99.9質量％以上，BET比表面積在3〜60m2/g之範圍內之 藉由使金屬鎂蒸氣與氧接觸而使金屬鎂蒸氣氧化之方法獲 得之氧化鎂粉末、MeO源粉末、EuO源粉末及Si02源粉 末之粉末混合物燒成而成， 3 (Me 1-X，Eux) Ο · aM g 0 · b S i 0 2 …⑴ 201202393 (但，式中，Me爲Sr，或者Ca及Ba中之一者或兩者與 Sr之混合物，X爲0.001〜0.110之範圍之數，a爲〇·9〜1.1 範圍之數，b爲1.8〜2.2範圍之數）。 上述本發明之製造方法之較佳樣態如下。 (1) 粉末混合物於將粉末混合物中之鎂量設爲1莫耳 時，含有換算成氯量爲0.02〜0.5莫耳之範圍之量之氯化 合物。 (2) 粉末混合物於將粉末混合物中之鎂量設爲1莫耳 時，含有換算成氯量爲0.02〜0.5莫耳之範圍之量之氯化 緦。 本發明進而有關以下述式（I)之組成式表示之矽酸鹽 系藍色發光螢光體， 3 (Me 1-X，Eux)0 · aMgO · bSi〇2 ... (I) (但，式中，Me爲Sr，或者Ca及Ba中之一者或兩者與 Sr之混合物，X爲0.001〜0.110之範圍之數，a爲0.9〜1.1 範圍之數，b爲1.8~2.2範圍之數）， 其以波長254ηηι之紫外線激發時發光之430~490nm 之波長範圍內之可見光之最大發光強度，相對於以波長 254nm 之紫外線激發（Ba〇.9 7 6，Eu〇.〇24)O.Mg0.5Al203 之 組成式表示之平均粒徑爲6.5 μηι之藍色發光螢光體時發光 之430〜490nm之波長範圍內之可見光之最大發光強度爲 1 . 1倍以上。 201202393 本發明之矽酸鹽系藍色發光螢光體之較佳樣態如下° (1) 前述式（I)中之Me爲Sr。 (2) 平均粒徑在1.0〜20μιη之範圍內。 (3) 係由上述本發明之製造方法所製得者。 [發明效果] 藉由利用本發明之製造方法，可工業上有利地製造以 波長254nm之紫外線激發時之藍色光發光強度顯著提高 之矽酸鹽系藍色發光螢光體。 本發明之矽酸鹽系藍色發光螢光體以波長25 4nm之 紫外線激發時之藍色光發光強度高，故而可有利地使用作 爲螢光燈之藍色光之發光源。 【實施方式】 由本發明之製造方法所得之矽酸鹽系藍色發光螢光體 係以下述式（I)之組成式表示。 3 (Me 1-x，Eux) Ο · aMgΟ · b S i 02 ... (I) 但，式中’ Me爲Sr，或者Ca及Ba中之一者或兩者 與Sr之混合物，χ爲 〇,ooi〜011〇之範圍之數，&爲 0.9〜1_1範圍之數’ b爲1.8〜2.2範圍之數。201202393 VI. Description of the Invention: [Technical Field] The present invention relates to a citrate-based blue luminescent phosphor which is particularly useful as a blue illuminating source for a fluorescent lamp and for producing the bismuth silicate blue An advantageous method of illuminating a phosphor. [Prior Art] In a light-emitting device that emits visible light and emits visible light by ultraviolet light (wavelength: 254 nm) generated by discharge of mercury vapor, etc., a blue light source has been widely used (Ba, An aluminate-based BAM blue luminescent phosphor represented by the general formula of Eu)0 · MgO · 5Al2〇3. However, the B AM blue luminescent phosphor has a problem that the luminescence intensity decreases with time. On the other hand, as a blue light-emitting phosphor having a small decrease in the intensity of light emission over time, it is known that 3 (Me, Eu) 0. aMgO · bSi02 (but Me is a group selected from Ca, Sr, and Ba) A blue-emitting phosphor of a citrate type represented by a general formula of one or more kinds of alkaline earth metals, a being a range of from 0.9 to 1.1, and b being a range of from 1.8 to 2.2. However, the citrate-based blue luminescent phosphor generally has a lower luminescence intensity than the aluminate-based BAM blue luminescent phosphor. Patent Document 1 describes a citrate-based blue containing an element such as Cu, Ga, Ge, As, Ag, Cd, In, Sn, Sb, Au, Hg, T1, Pb, or Bi as an additive element in the matrix. A luminescent phosphor having a high luminescence intensity when excited by a vacuum ultraviolet ray having a wavelength of 147 nm. Further, in the embodiment of Patent Document 1, by using SrC03 as the MeO source, 201202393 using MgC03 as the MgO source, SiO2 as the SiO2 source, Eu203 as the EuO source, and NH4Br as the melting aid (flux). The powder mixture is fired to produce a citrate-based blue luminescent phosphor. Patent Document 2 mainly discloses a citrate-based blue luminescent phosphor in which a part of Mg is substituted with a metal selected from the group consisting of elements of Group 5 and Group 6, and is irradiated with a vacuum ultraviolet ray having a wavelength of 146 nm. The luminous intensity was improved at 1 hour and 24 hours. Further, in the embodiment of Patent Document 2, cesium carbonate and cesium carbonate are used as the MeO source, alkaline magnesium carbonate is used as the MgO source, cerium oxide is used as the SiO 2 source, and cerium oxide is used as the powder mixture of the EuO source. Thus, a citrate-based blue luminescent phosphor is produced. [Prior Art] [Patent Document] Patent Document 1: JP-A-2006-70, No. JP-A No. JP-A No. 2007-70 No. Although various investigations have been made for the purpose of improving the light-emitting intensity of the light-emitting element of the phthalate-based blue light-emitting phosphor, the citrate-based blue light-emitting phosphor which has hitherto been known has been specifically studied according to the present inventors. It is the luminous intensity at the time of ultraviolet excitation at a wavelength of 25 4 nm. Compared with the BAM blue phosphor, 尙 cannot be said to have been sufficiently improved. .201202393 Therefore, the object of the present invention is to provide a citrate-based blue luminescent phosphor having improved luminescence intensity when excited by ultraviolet rays having a wavelength of 254 nm and a method for producing the same. [Means for Solving the Problem] The present inventors have found that when a powder mixture containing a MeO source powder, an EuO source powder, a MeO source powder, and a SiO 2 source powder is fired to produce a citrate-based blue luminescent phosphor, The MgO source is a high-purity fine magnesium oxide powder obtained by a method in which metal magnesium vapor is brought into contact with oxygen to oxidize magnesium metal vapor, or a high-purity fine alkaline magnesium carbonate powder is used in a MgO source, and further in a powder mixture. A specific amount of a chlorine compound is added as a flux, whereby the obtained phthalate-based blue luminescent phosphor is improved in luminescence intensity when excited by ultraviolet light having a wavelength of 2 54 nm, and in particular, BAM having an illuminating intensity of aluminate can be obtained. The novel citrate-based blue luminescent phosphor in which the blue luminescent phosphor is 1.1 times or more the luminescence intensity when excited by ultraviolet rays having a wavelength of 254 nm, has completed the present invention. Therefore, the method for producing a phthalate-based blue luminescent phosphor represented by the following formula (I) of the present invention is characterized in that the purity is 99.9% by mass or more and the BET specific surface area is 3 to 60 m 2 / A powder mixture of magnesium oxide powder, MeO source powder, EuO source powder and SiO2 source powder obtained by a method in which magnesium metal vapor is brought into contact with oxygen by contacting magnesium metal vapor with a metal, and 3 (Me) 1-X,Eux) Ο · aM g 0 · b S i 0 2 (1) 201202393 (However, in the formula, Me is Sr, or one of Ca and Ba or a mixture of both and Sr, X is 0.001~ For the range of 0.110, a is the range of 〇·9 to 1.1, and b is the number ranging from 1.8 to 2.2). The preferred embodiment of the above manufacturing method of the present invention is as follows. (1) When the amount of magnesium in the powder mixture is 1 mol, the powder mixture contains a chloride compound in an amount in the range of 0.02 to 0.5 mol. (2) The powder mixture contains cerium chloride in an amount of from 0.02 to 0.5 mol in terms of chlorine in an amount of 1 mol of the powder mixture. Further, the present invention relates to a citrate-based blue luminescent phosphor represented by the following formula (I), 3 (Me 1-X, Eux) 0 · aMgO · bSi 〇 2 (I) (but Wherein Me is Sr, or one of Ca and Ba or a mixture of both and Sr, X is in the range of 0.001 to 0.110, a is in the range of 0.9 to 1.1, and b is in the range of 1.8 to 2.2. The maximum luminous intensity of visible light in the wavelength range of 430 to 490 nm when excited by ultraviolet light having a wavelength of 254 ηηι is excited with respect to ultraviolet light having a wavelength of 254 nm (Ba〇.9 7 6, Eu 〇. 〇 24) The composition of the formula of Mg0.5Al203 indicates that the maximum luminescence intensity of visible light in the wavelength range of 430 to 490 nm when the average particle diameter of the blue luminescent phosphor is 6.5 μηι is 1.1 times or more. 201202393 The preferred embodiment of the phthalate-based blue luminescent phosphor of the present invention is as follows: (1) Me in the above formula (I) is Sr. (2) The average particle diameter is in the range of 1.0 to 20 μm. (3) It is produced by the above-described production method of the present invention. [Effect of the Invention] By using the production method of the present invention, a citrate-based blue light-emitting phosphor having a markedly improved blue light-emitting intensity when excited by ultraviolet rays having a wavelength of 254 nm can be industrially advantageously produced. The bismuth silicate-based blue luminescent phosphor of the present invention has a high luminescence intensity when excited by ultraviolet light having a wavelength of 25 4 nm, so that a luminescence source as a blue light of a fluorescent lamp can be advantageously used. [Examples] The citrate-based blue luminescent phosphor obtained by the production method of the present invention is represented by the following formula (I). 3 (Me 1-x,Eux) Ο · aMgΟ · b S i 02 (I) However, in the formula, 'Me is Sr, or one of Ca and Ba or a mixture of both and Sr, 〇, the number of ooi~011〇 range, & is the range of 0.9~1_1' b is the range of 1.8~2.2.
Me較好爲Sr ’或爲Ba與Sr之混合物，最好爲Sr。 Ba與Sr之混合物以Ba之含量爲i莫耳時Sr之含量較好 201202393 在3〜6莫耳之範圍內。 X較好爲 0.010〜0.070之範圍之數。a較好爲 0.97〜1.03範圍之數。b較好爲1.97〜2.03範圍之數。 本發明之矽酸鹽系藍色發光螢光體之製造方法，有於 矽酸鹽系藍色發光螢光體之MgO源粉末使用氧化鎂粉末 之方法以及使用鹼性碳酸鎂粉末之方法。首先，針對於 MgO源粉末使用氧化鎂粉末之方法加以說明。 作爲MgO源粉末使用之氧化鎂粉末爲純度爲99.9質 量％以上，BET比表面積在3~60m2/g之範圍內之藉由使 金屬鎂蒸氣與氧接觸而使金屬鎂蒸氣氧化之方法（氣相法） 獲得之氧化鎂粉末。亦即，係高純度且由下式計算式求得 之BET徑在0.02 8~0.56μπι之範圍內之微細氧化鎂粉末。 氧化鎂粉末之BET比表面積較好在5〜45m2/g之範圍內， 最好在5〜20m2/g之範圍內。 BET 徑（μηι) = 6/ [ΒΕΤ 比表面積（m2/g)x3_58(g/cm3)] 上述計算式中，6表示表面形狀係數，3.58g/cm3爲 氧化鎂粉末之真密度。 由氣相法所得之氧化鎂粉末其一次粒子形狀爲立方體 狀，難以形成凝集粒子。因此，藉由於MgO源粉末使用 由氣相法所得之氧化鎂粉末，可成爲氧化鎂粉末均一分散 之矽 高之 性 高 1 度 均強 成光 組發 其的 使一 由均 藉成 ’ 組 物得 合獲 混可 末’ 粉成 之燒 高以 性予 1 物 均合 成混 組末 且粉 -10- 201202393 酸鹽系藍色發光螢光體。Me is preferably Sr ' or a mixture of Ba and Sr, preferably Sr. The mixture of Ba and Sr is preferably in the range of 3 to 6 moles when the content of Ba is i mole. X is preferably in the range of 0.010 to 0.070. a is preferably in the range of 0.97 to 1.03. b is preferably in the range of 1.97 to 2.03. The method for producing a phthalate-based blue luminescent phosphor of the present invention comprises a method of using a magnesium oxide powder for a MgO source powder of a phthalate-based blue luminescent phosphor, and a method of using a basic magnesium carbonate powder. First, a method of using magnesium oxide powder as a powder of MgO source will be described. The magnesium oxide powder used as the MgO source powder is a method in which the magnesium magnesium vapor is oxidized by contacting the metal magnesium vapor with oxygen by having a purity of 99.9% by mass or more and a BET specific surface area of 3 to 60 m 2 /g. Method) Obtained magnesium oxide powder. Namely, it is a fine magnesium oxide powder having a high purity and having a BET diameter of from 0.02 to 0.56 μm as determined by the following formula. The BET specific surface area of the magnesium oxide powder is preferably in the range of 5 to 45 m 2 /g, preferably in the range of 5 to 20 m 2 /g. BET diameter (μηι) = 6/ [ΒΕΤ specific surface area (m2/g) x3_58 (g/cm3)] In the above formula, 6 represents the surface shape factor, and 3.58 g/cm3 is the true density of the magnesium oxide powder. The magnesium oxide powder obtained by the vapor phase method has a cubic particle shape in a primary particle shape, and it is difficult to form aggregated particles. Therefore, since the magnesium oxide powder obtained by the vapor phase method is used as the MgO source powder, the magnesium oxide powder can be uniformly dispersed, and the high-strength property is 1 degree, and the light is formed into a light group. It is obtained by mixing and mixing the powder. The powder is high in the properties of the powder. The compound is mixed with the powder and the powder is -10-201202393.
MgO源粉末以外之原料粉末，亦即Me0源粉末、 EuO源粉末及Si〇2源粉末可爲氧化物之粉末，亦可爲使 氫氧化物、鹵化物、碳酸鹽、硝酸鹽及草酸鹽等利用加熱 而生成氧化物之化合物之粉末。該等原料粉末較好純度爲 9 9質.量％以上，更好爲99.9質量％以上。且，平均粒徑較 好在0.1 ~5 0μιη之範圍內。且，本說明書中，平均粒徑係 利用雷射繞射散射法測定之値。 粉末混合物中’爲了更提闻所得砂酸鹽系藍色發光蛋 光體之最大發光強度，亦可添加W、Pb、Ρ等之元素。該 等元素之添加量，於MgO源中之鎂量作爲i莫耳時，較 好在0.01〜0.2莫耳之範圍內之量》 粉末混合物較好作成平均粒徑於1 0〜80μιη之範圍內 之粒狀體後予以燒成。粉末混合物之粒狀體可使用將各原 料粉末於水中混合，作成粉末混合物之漿料後，將漿料噴 霧乾燥之方法而製造。 粉末混合物較好添加助熔劑•助熔劑較好爲氯化合物 。氯化合物之添加量於將粉末混合物中之鎂量作爲1莫耳 時，換算成氯量較好在〇.〇2〜0.5莫耳之範圍內，更好在 0_1〜0.5莫耳之範圍內，最好在0.2〜0.5莫耳之範圍內。 氯化合物較好爲構成矽酸鹽系藍色發光蛮光體之金屬 (Me、Eu、Mg)之氯化物。氯化合物之例可舉例爲氯化緦 、氯化鎂、氯化銪。氯化合物較好爲氯化緦。 粉末混合物之燒成較好在還原性氣體氛圍下進行。還 -11 - 201202393 原性氣體之例可舉例爲0.5〜5.0體積％之氫氣與99.5〜95.0 體積％之惰性氣體之混合氣體。惰性氣體之例可舉例爲氬 氣及氮氣。燒成溫度一般爲900〜130CTC之範圍，較好爲 1 05 0〜125(TC之範圍，最好爲1100~123(TC之範圍。燒成 時間一般爲〇 . 5〜1 0 0小時之範圍。 於原料粉末使用利用加熱而生成氧化物之化合物粉末 時，在還原性氣體氛圍下燒成之前，較好使粉末混合物在 大氣氛圍下，於600〜850°C之溫度預鍛燒0.5〜100小時。 利用燒成所得之矽酸鹽系藍色發光螢光體，依據需要 亦可進行分級處理、利用鹽酸或硝酸等之無機酸之酸洗淨 處理、烘烤處理。 接著，針對MgO源粉末使用鹼性碳酸鎂粉末之方法 加以說明。 作爲MgO源粉末使用之鹼性碳酸鎂粉末，其純度爲 99質量％以上，平均粒徑在1〜20μιη之範圍內。於MgO 源粉末使用鹼性碳酸鎂粉末時，使用氯化合物爲助熔劑， 原料粉末之粉末混合物中之氯化合物，以鎂量作爲1莫耳 時，較好以換算成氯量爲0.2〜0.5莫耳之範圍之量添加。 除此以外，與MgO源粉末使用鎂粉末之情況相同。 藉由使用上述製造方法，可獲得比鋁酸鹽之BAM藍 色發光體之以波長254nm之紫外線激發時之發光強度更 大之矽酸鹽系藍色發光螢光體，尤其是以波長25 4nm之 紫外線激發時發光之43 0〜490nm之波長範圍內之可見光 之最大發光強度，相對於以波長254nm之紫外線激發 -12- 201202393 (Bao.9 7 6，EuG.Q24) Ο · MgO · 5Al2〇3之組成式表示之平均粒 徑爲6.5μιη之BAM藍色發光螢光體時發光之430〜490nm 之波長範圍內之可見光之最大發光強度爲1.1倍以上之新 穎矽酸鹽系藍色發光螢光體。該矽酸鹽系藍色發光螢光體 相對於BAM藍色發光螢光體之最大發光強度之倍率較好 爲1.3倍以上，通常爲2.0倍以下，尤其是1.8倍以下。 又，本說明書中，最大發光強度意指在430〜490nm之波 長範圍內之可見光之發光峰中最高發光峰之高度。 上述矽酸鹽系藍色發光螢光體較好平均粒徑（利用雷 射繞射散射法測定之値）在1.0〜20μηι之範圍內。 實施例 以下，利用實施例及比較例說明本發明。又’實施例 及比較例中，最大發光強度爲相對於以（Bao.976，EU0.0 24 ) 0.Mg0.5Al203之組成物表示之平均粒徑爲6·5μηι之鋁 酸鹽系之ΒΑΜ藍色發光螢光體以波長254nm之紫外線激 發時發光之43 0〜490nm之波長範圍內之可見光之最大發 光強度之倍率。 [實施例1] 將碳酸緦粉末[SrC03 :純度99.99質量％，平均粒徑 2·73μιη]、氯化鋸粉末[SrCl2 :純度99.99質量、氧化鎂 粉末[MgO :利用氣相法製造者，純度99.98質量％以上’ BET比表面積8m2/g(BET徑0.20μιη)]、氧化矽粉末[Si〇2 -13- 201202393 :純度 99.9質量％，平均粒徑 3.87μΐη]、氧化銪粉末 [Eu203:純度99.9質量％，平均粒徑2.71μπι]之各原料粉 末，以莫耳比爲 2.860 : 0.125 : 1.000 : 2.000 : 0.01 50( = SrCO3 : SrCl2 : MgO : Si02 : Eu203)之比例予以 砰量。 將所秤量之各原料粉末與純水一起饋入球磨機中，濕 式混合24小時，獲得粉末混合物之漿料。所得漿料利用 噴霧乾燥機噴霧乾燥，獲得平均粒徑爲40μηι之粉末混合 物粒狀體。將所得粉末混合物粒狀體置入氧化鋁坩堝中， 在大氣氛圍下以800°C之溫度預鍛燒3小時，接著放冷至 室溫後，在2體積％氫氣-98體積％氬氣之還原性氛圍下在 1 200 °C之溫度燒成 3小時，獲得組成物以 3(Sr2.9 9 5 , Euo.ooOO· MgO· Si02表示之矽酸鹽系藍色發光螢光體。 所得矽酸鹽系藍色發光螢光體利用網眼20μπι之聚醯胺製 篩進行濕式過篩，去除粗大粒子後，予以乾燥。去除粗大 粒子後之矽酸鹽系藍色發光螢光體之平均粒徑爲7μπι。 將所得之矽酸鹽系藍色發光螢光體形成爲層狀，對該 矽酸鹽系藍色發光螢光體照射波長25 4nm之紫外線後， 顯示最大峰波長爲4 6 Onm之藍色光發光，由其最大峰求 得之最大發光強度爲1 . 3 5倍。 [實施例2] 除將粉末混合物粒狀體在還原性氛圍下之燒成溫度設 爲1100°c以外，餘與實施例1同樣獲得矽酸鹽系藍色發 -14- 201202393 光螢光體。所得矽酸鹽系藍色發光螢光體之平均粒徑爲 4μηι。對該矽酸鹽系藍色發光螢光體與實施例1相同以波 長254nm之紫外線照射後，顯示最大峰波長爲460nm之 藍色光發光’由其最大峰求得之最大發光強度爲1.32倍 [實施例3] 除將粉末混合物粒狀體在還原性氛圍下之燒成溫度設 爲1 220°C以外，餘與實施例1同樣獲得矽酸鹽系藍色發 光螢光體。所得矽酸鹽系藍色發光螢光體之平均粒徑爲 9μηι。對該矽酸鹽系藍色發光螢光體與實施例1相同以波 長254nm之紫外線照射後，顯示最大峰波長爲460nm之 藍色光發光，由其最大峰求得之最大發光強度爲1.34倍 [實施例4] 替代氧化鎂粉末，而使用鹼性碳酸鎂[41^1§(：03· Mg(OH)2 . 4H20 : Aldrich 公司製造，純度：99 質量 ％， 平均粒徑：1 3 .5 μηι]，將碳酸緦粉末、氯化緦粉末、鹼性 碳酸鎂粉末、氧化矽粉末及氧化銪粉末之各原料粉末，改 爲以莫耳比爲 2.860: 0.1 25： 1.00： 0.20： 0.0150( = SrC03 :SrCh : 4MgC03 · Mg(OH)2 . 4H20 : Si〇2 : Eu203)之比 例以外，與實施例1同樣獲得矽酸鹽系藍色發光螢光體。 所得矽酸鹽系藍色發光螢光體之平均粒徑爲9μιη。對該矽 -15- 201202393 酸鹽系藍色發光螢光體與實施例1相同以波長254nm之 紫外線照射後，顯示最大峰波長爲46Onm之藍色光發光 ’由其最大峰求得之最大發光強度爲1.15倍。 [比較例1 ] 除將碳酸緦粉末、鹼性碳酸鎂粉末、氧化矽粉末及氧 化銪粉末之各原料粉末之混合量，以莫耳比設爲2.98 5: 1.00 : 2.00 ： 0.015( = SrC03 : MgO : Si02 : Eu203)之比例 ，而不使用氯化錁粉末以外，與實施例4同樣獲得矽酸鹽 系藍色發光螢光體。所得矽酸鹽系藍色發光螢光體之平均 粒徑爲8μιη。對該矽酸鹽系藍色發光螢光體與實施例1相 同以波長254nm之紫外線照射後，雖顯示最大峰波長爲 4 6Onm之藍色光發光，但由其最大峰求得之最大發光強度 爲0.9倍，爲低於基準的BAM藍色發光螢光體之値^ -16-The raw material powder other than the MgO source powder, that is, the Me0 source powder, the EuO source powder, and the Si〇2 source powder may be an oxide powder, or may be a hydroxide, a halide, a carbonate, a nitrate, and an oxalate. A powder of a compound which forms an oxide by heating. The raw material powder preferably has a purity of 99% by mass or more, more preferably 99.9% by mass or more. Further, the average particle diameter is preferably in the range of 0.1 to 50 μm. Further, in the present specification, the average particle diameter is measured by a laser diffraction scattering method. In the powder mixture, in order to further improve the maximum luminescence intensity of the obtained sulphate-based blue luminescent egg, an element such as W, Pb or yttrium may be added. The amount of the elements added is preferably in the range of 0.01 to 0.2 moles when the amount of magnesium in the MgO source is i moles. The powder mixture is preferably formed to have an average particle diameter of from 10 to 80 μm. The granular body is fired. The granules of the powder mixture can be produced by mixing the raw material powders in water to form a slurry of the powder mixture, and then drying the slurry by a spray drying method. Preferably, the powder mixture is preferably added with a fluxing agent. The fluxing agent is preferably a chlorine compound. When the amount of the chlorine compound is 1 mol per kg of the powder mixture, the amount of chlorine is preferably in the range of 〇.〇2 to 0.5 mol, more preferably in the range of 0_1 to 0.5 mol. It is preferably in the range of 0.2 to 0.5 moles. The chlorine compound is preferably a chloride of a metal (Me, Eu, Mg) constituting a citrate-based blue luminescent body. Examples of the chlorine compound are ruthenium chloride, magnesium chloride, and ruthenium chloride. The chlorine compound is preferably ruthenium chloride. The firing of the powder mixture is preferably carried out under a reducing gas atmosphere. Further, -11 - 201202393 An example of the raw gas can be exemplified by a mixed gas of 0.5 to 5.0% by volume of hydrogen and 99.5 to 95.0% by volume of an inert gas. Examples of the inert gas are argon gas and nitrogen gas. The firing temperature is generally in the range of 900 to 130 CTC, preferably in the range of 1500 to 125 (TC range, preferably 1100 to 123 (the range of TC. The firing time is generally 〇. 5 to 1 0 0 range). When the compound powder which generates an oxide by heating is used as the raw material powder, it is preferred to pre-calcin the powder mixture at a temperature of 600 to 850 ° C in an atmosphere of 0.5 to 100 before firing in a reducing gas atmosphere. The phthalate-based blue luminescent phosphor obtained by calcination may be subjected to classification treatment or acid cleaning treatment or baking treatment using a mineral acid such as hydrochloric acid or nitric acid, if necessary. Next, for the MgO source powder The method of using a basic magnesium carbonate powder is described. The basic magnesium carbonate powder used as the MgO source powder has a purity of 99% by mass or more and an average particle diameter of 1 to 20 μm. The alkaline carbonic acid is used for the MgO source powder. In the case of the magnesium powder, the chlorine compound is used as the flux, and the chlorine compound in the powder mixture of the raw material powder is preferably added in an amount of 0.2 to 0.5 mol per equivalent of the amount of chlorine when the amount of magnesium is 1 mol. this In addition, it is the same as the case where the magnesium powder is used as the powder of the MgO source. By using the above-described production method, a citrate system having a higher luminescence intensity when excited by ultraviolet rays having a wavelength of 254 nm than the BAM blue illuminant of the aluminate can be obtained. The blue luminescent phosphor, especially the maximum luminescence intensity of visible light in the wavelength range of 43 0 to 490 nm when excited by ultraviolet light having a wavelength of 25 4 nm, is excited with respect to ultraviolet light having a wavelength of 254 nm -12-201202393 (Bao.9 7 6, EuG.Q24) Ο · The composition of MgO · 5Al2〇3 indicates that the maximum luminescence intensity of visible light in the wavelength range of 430 to 490 nm when the BAM blue luminescent phosphor having an average particle diameter of 6.5 μm is 1.1 times or more of the novel citrate-based blue luminescent phosphor. The ratio of the maximum luminescence intensity of the phthalate-based blue luminescent phosphor to the BAM blue luminescent phosphor is preferably 1.3 times or more, usually Further, it is 2.0 times or less, especially 1.8 times or less. In addition, in the present specification, the maximum luminescence intensity means the height of the highest luminescence peak among the luminescence peaks of visible light in the wavelength range of 430 to 490 nm. The preferred average particle diameter (measured by a laser diffraction scattering method) of the photoluminescence is in the range of 1.0 to 20 μm. EXAMPLES Hereinafter, the present invention will be described by way of Examples and Comparative Examples. Further, Examples and Comparative Examples The maximum luminescence intensity is an aluminosilicate-based indigo luminescent phosphor having an average particle diameter of 6·5 μηι represented by a composition of (Bao.976, EU0.0 24 ) 0.Mg0.5Al203 The magnification of the maximum luminous intensity of visible light in the wavelength range of 43 0 to 490 nm when the ultraviolet light is excited at a wavelength of 254 nm. [Example 1] strontium carbonate powder [SrC03: purity: 99.99% by mass, average particle diameter: 2.73 μm], chlorinated saw powder [SrCl2: purity: 99.99 mass, magnesium oxide powder [MgO: manufactured by gas phase method, purity) 99.98 mass% or more 'BET specific surface area 8 m2/g (BET diameter 0.20 μιη)), cerium oxide powder [Si〇2 -13-201202393: purity 99.9% by mass, average particle diameter 3.87 μΐη], cerium oxide powder [Eu203: purity Each of the raw material powders having a mass ratio of 2.99 mass% and an average particle diameter of 2.71 μm was subjected to a molar ratio of 2.860 : 0.125 : 1.000 : 2.000 : 0.01 50 ( = SrCO 3 : SrCl 2 : MgO : Si02 : Eu203). Each of the weighed raw material powders was fed into a ball mill together with pure water, and wet-mixed for 24 hours to obtain a slurry of the powder mixture. The resulting slurry was spray-dried by a spray dryer to obtain a powder mixture granule having an average particle diameter of 40 μm. The obtained powder mixture granules were placed in an alumina crucible, pre-calcined at 800 ° C for 3 hours under an atmosphere, and then cooled to room temperature, after 2 vol% hydrogen - 98 vol% argon gas. The mixture was fired at a temperature of 1,200 ° C for 3 hours in a reducing atmosphere to obtain a phthalate-based blue luminescent phosphor represented by 3 (Sr2.9 9 5 , Euo.ooOO·MgO·SiO 2 ). The acid-based blue luminescent phosphor is wet-screened by a mesh of 20 μm polyamide, and the coarse particles are removed and dried. The average of the citrate-based blue luminescent phosphor after removing the coarse particles is removed. The particle size is 7 μm. The obtained citrate-based blue light-emitting phosphor is formed into a layer, and the strontium-based blue light-emitting phosphor is irradiated with ultraviolet light having a wavelength of 25 4 nm, and the maximum peak wavelength is 4 6 Onm. The blue light is emitted, and the maximum luminous intensity obtained from the maximum peak is 135 times. [Example 2] Except that the firing temperature of the powder mixture granules in a reducing atmosphere is set to 1100 ° C, In the same manner as in Example 1, a phthalate-based blue hair-14-201202393 light phosphor was obtained. The obtained citrate-based blue luminescent phosphor had an average particle diameter of 4 μm. The citrate-based blue luminescent phosphor was irradiated with ultraviolet light having a wavelength of 254 nm in the same manner as in Example 1, and showed a maximum peak wavelength of 460 nm. The maximum luminous intensity obtained by the maximum peak of the blue light emission is 1.32 times [Example 3] Except that the firing temperature of the powder mixture granules in a reducing atmosphere is set to 1 220 ° C, the remainder and the examples 1 A phthalate-based blue luminescent phosphor was obtained in the same manner, and the obtained citrate-based blue luminescent phosphor had an average particle diameter of 9 μm. The citrate-based blue luminescent phosphor was the same as in Example 1. After ultraviolet irradiation at a wavelength of 254 nm, blue light emission having a maximum peak wavelength of 460 nm was observed, and the maximum luminous intensity obtained from the maximum peak was 1.34 times [Example 4] Instead of magnesium oxide powder, alkaline magnesium carbonate was used [41^ 1§(:03·Mg(OH)2 . 4H20 : Manufactured by Aldrich, purity: 99% by mass, average particle size: 1 3 .5 μηι], barium carbonate powder, barium chloride powder, basic magnesium carbonate powder , raw materials powder of cerium oxide powder and cerium oxide powder, The tannic acid was obtained in the same manner as in Example 1 except that the molar ratio was 2.860: 0.1 25: 1.00: 0.20: 0.0150 (= SrC03: SrCh: 4MgC03 · Mg(OH) 2 .4H20 : Si〇 2 : Eu203). a salt-based blue light-emitting phosphor. The obtained citrate-based blue light-emitting phosphor has an average particle diameter of 9 μm. The 矽-15-201202393 acid-based blue light-emitting phosphor is the same wavelength as in Example 1. After ultraviolet irradiation at 254 nm, the blue light emission showing a maximum peak wavelength of 46 Onm was found to have a maximum luminous intensity of 1.15 times from its maximum peak. [Comparative Example 1] The mixing amount of each of the raw material powders of the cerium carbonate powder, the basic magnesium carbonate powder, the cerium oxide powder, and the cerium oxide powder was set to 2.98 5: 1.00 : 2.00 : 0.015 ( = SrC03 : A citrate-based blue luminescent phosphor was obtained in the same manner as in Example 4 except that the cerium chloride powder was used in a ratio of MgO : SiO 2 : Eu 203 . The obtained citrate-based blue luminescent phosphor had an average particle diameter of 8 μm. This citrate-based blue luminescent phosphor was irradiated with ultraviolet light having a wavelength of 254 nm in the same manner as in Example 1, and showed a blue light emission having a maximum peak wavelength of 46 nm, but the maximum luminescence intensity obtained from the maximum peak was 0.9 times, which is below the benchmark BAM blue luminescent phosphor ^ -16-